EP0086375B1 - Pyridine derivatives, their preparation and use - Google Patents

Pyridine derivatives, their preparation and use Download PDF

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Publication number
EP0086375B1
EP0086375B1 EP83100757A EP83100757A EP0086375B1 EP 0086375 B1 EP0086375 B1 EP 0086375B1 EP 83100757 A EP83100757 A EP 83100757A EP 83100757 A EP83100757 A EP 83100757A EP 0086375 B1 EP0086375 B1 EP 0086375B1
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Prior art keywords
compounds
chlorine
carbon atoms
compound
alkyl
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EP83100757A
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German (de)
French (fr)
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EP0086375A3 (en
EP0086375A2 (en
Inventor
Rudolf Dr. Dipl.-Chem. Mengel
Ludwig Dr. Dipl.-Chem. Schröder
Werner Dr. Dipl.-Chem. Stransky
Gerbert Dr. Dipl.-Landwirt Linden
Sigmund Dr. Lust
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Shell Internationale Research Maatschappij BV
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Celamerck GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4

Definitions

  • aliphatic radicals contain 3 or 4 carbon atoms, they can be unbranched or branched.
  • CF 3 and CCI 3 are particularly to be mentioned as fluorine- or chlorine-substituted alkyl radicals.
  • the compounds of the invention are distinguished by a strong action against numerous monocot and dicot weeds, for. B. also difficult to control such as Galium aparine, Verinica hederifolia. Also of considerable benefit is the opportunity to close in practice significant gaps in the effectiveness of many otherwise well-proven commercial products by using the new active ingredients together with them.
  • Combination partners of this type are, for example: chlorotoluron and related urea derivatives, terbutryn and related triazine derivatives, trifluralin and related derivatives, alachlor, dimethachlor and related compounds.
  • the new compounds are prepared in a manner known per se.
  • the reaction of the compounds II and Illa or III b takes place at temperatures between the ambient temperature and about 160 ° C. It is preferably carried out in polar solvents such as acetone, butan-2-one, acetonitrile, dimethylformamide, dimethyl sulfoxide at room temperature or moderately elevated temperature.
  • polar solvents such as acetone, butan-2-one, acetonitrile, dimethylformamide, dimethyl sulfoxide at room temperature or moderately elevated temperature.
  • alkali metal carbonates such as Na 2 CO 3, K 2 C0 3, or alkali or alkaline earth (NaOH, KOH, Ca (OH) 2 supply in order to achieve a favorable yield, it may be advantageous to use the phenol or its salts and / or the acid-binding agent in excess.
  • the starting materials of the formulas II, Illa and Illb are known or can be obtained analogously to the known compounds.
  • the compounds of the formula are processed into customary formulations for use in crop protection with customary auxiliaries and / or carriers.
  • the concentrates specified under a) to c) are diluted with water to about 0.05 to 5 percent by weight for use.
  • the application can take place both before and after emergence. If the new active ingredients are used alone, this is preferably done before emergence.
  • Protons in the pyridine part 1 proton at 8.22 ppm, 2 protons at 6.71.
  • the cleaned product is a light oil; Yield 1.4 g (38% of theory).
  • Rf value 0.48 ready-made DC plates from E. MERCK, Darmstadt, with silica gel 60-F-254. Solvent acetone / diisopropyl ether 1: 2; the spots are visible in ultraviolet light at 254 ⁇ m).
  • the DC prefabricated plates of the type used here and the uv light of the stated wavelength also served to determine the other Rf values.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

Compounds of the formula <IMAGE> wherein W and X, which may be identical to or different from each other, are each hydrogen, fluorine, chlorine, bromine, iodine, nitro, alkyl of 1 to 4 carbon atoms, fluoro-substituted alkyl of 1 to 4 carbon atoms or chloro-substituted alkyl of 1 to 4 carbon atoms; Y is hydrogen, fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms, fluoro-substituted alkyl of 1 to 4 carbon atoms or chloro-substituted alkyl of 1 to 4 carbon atoms; Z is fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms, fluoro-substituted alkyl of 1 to 4 carbon atoms, chloro-substituted alkyl of 1 to 4 carbon atoms, -COOH or -COO-(alkyl of 1 to 4 carbon atoms); and n is 0 or 1; and, when Z is COOH, salts thereof, especially their alkali metal salts. The compunds as well as the salts are useful as selective herbicides.

Description

Die Erfindung betrifft neue Pyridinderivate der Formel herbizid wirksame phenoxysubstituierte Pyridine der allgemeinen Formel

Figure imgb0001
in der

  • W und R, die gleich oder verschieden sein können, für H, F, CI, Br, J, N02 oder einen gegebenenfalls fluor- oder chlorsubstituierten C1-C4-Alkylrest,
  • Y für H, F, CI, Br oder einen gegebenenfalls fluor- oder chlorsubstituierten Cl-C4-Alkylrest,
  • Z für F, Cl, Br, einen gegebenenfalls fluor- oder chlorsubstithierten C1-C4-Alkylrest oder COOH oder COO- (C1-C4-Alkyl)

und
  • n für 0 oder 1 steht,
  • die Herstellung der neuen Verbindungen und ihre Verwendung als biozide, insbesondere herbizide Wirkstoffe.
The invention relates to new pyridine derivatives of the formula herbicidally active phenoxy-substituted pyridines of the general formula
Figure imgb0001
 in the
  • W and R, which may be the same or different, represent H, F, CI, Br, J, N0 2 or an optionally fluorine- or chlorine-substituted C 1 -C 4 -alkyl radical,
  • Y represents H, F, CI, Br or an optionally fluorine- or chlorine-substituted C 1 -C 4 -alkyl radical,
  • Z represents F, Cl, Br, an optionally fluorine- or chlorine-substituted C 1 -C 4 alkyl radical or COOH or COO- (C 1 -C 4 alkyl)

and
  • n represents 0 or 1,
  • the preparation of the new compounds and their use as biocidal, in particular herbicidal active substances.

Soweit die aliphatischen Reste 3 oder 4 C-Atome enthalten, können sie unverzweigt oder verzweigt sein. Als fluor- oder chlorsubstituierte Alkylreste sind vor allem CF3 und CCI3 zu nennen.If the aliphatic radicals contain 3 or 4 carbon atoms, they can be unbranched or branched. CF 3 and CCI 3 are particularly to be mentioned as fluorine- or chlorine-substituted alkyl radicals.

Als bevorzugte Substituentenbedeutungen sind zu nennen:

  • W gleich H, CI, F, CH3, CF3, N02;
  • X gleich H, F, CI, CH3, CF3, N02;
  • Y gleich H, F, Cl, CF3, CCI3, CH3;
  • Z gleich F,-CI, CF3, CH3, COOH, COOCH3. CO0C2H5
  • n steht bevorzugt für 0.
The preferred substituent meanings are:
  • W is H, CI, F, CH 3 , CF 3 , N0 2 ;
  • X is H, F, CI, CH 3 , CF 3 , N0 2 ;
  • Y is H, F, Cl, CF 3 , CCI 3 , CH 3 ;
  • Z is F, -CI, CF 3 , CH 3 , COOH, COOCH 3 . CO0C 2 H 5
  • n is preferably 0.

Im Falle Z = COOH können die neuen Säuren auch als Salze, insbesondere als Alkalisalze vorliegen.

  • Aus der DE-OS 15 42 736 sind

aryloxysubstituierte Pyridine bekannt, die der allgemeinen Formel
Figure imgb0002
 In the case of Z = COOH, the new acids can also be present as salts, in particular as alkali salts.
  • From DE-OS 15 42 736 are

Aryloxy-substituted pyridines known to have the general formula
Figure imgb0002

entsprechen. Diese Verbindungen, die im Pyridinring keinen zusätzlichen Substituenten aufweisen - beispielsweise die besonders herausgestellte Verbindung 4-(2',4'-Dichlorphenoxy)-pyridin-sind herbizid wirksam.correspond. These compounds, which have no additional substituents in the pyridine ring - for example the particularly emphasized compound 4- (2 ', 4'-dichlorophenoxy) pyridine - are herbicidally active.

Außerdem sind aus der US-PS 35 76 616

Figure imgb0003
In addition, from US-PS 35 76 616
Figure imgb0003

bekannt die im Pyridinteil mindestens einfach mit Fluor, Chlor oder Brom und im Phenoxyteil ein- oder mehrfach mit Chlor oder Brom substituiert sind.are known which are substituted at least once in the pyridine part with fluorine, chlorine or bromine and in the phenoxy part one or more times with chlorine or bromine.

Die erfindungsgemäßen Verbindungen zeichnen sich demgegenüber aus durch eine starke Wirkung gegen zahlreiche monokotyle und dikotyle Unkräuter z. B. auch schwer bekämpfbare wie Galium aparine, Verinica hederifolia. Von erheblichem Nutzen ist auch die Möglichkeit, für die Praxis bedeutsame Wirkungslücken vieler sonst sehr bewährter Handelsprodukte zu schließen, indem man die neuen Wirkstoffe gemeinsam mit ihnen anwendet.The compounds of the invention are distinguished by a strong action against numerous monocot and dicot weeds, for. B. also difficult to control such as Galium aparine, Verinica hederifolia. Also of considerable benefit is the opportunity to close in practice significant gaps in the effectiveness of many otherwise well-proven commercial products by using the new active ingredients together with them.

Kombinationspartner dieser Art sind beispielsweise: Chlortoluron und verwandte Harnstoffderivate, Terbutryn und verwandte Triazinderivate, Trifluralin und verwandte Derivate, Alachlor, Dimethachlor und verwandte Verbindungen.Combination partners of this type are, for example: chlorotoluron and related urea derivatives, terbutryn and related triazine derivatives, trifluralin and related derivatives, alachlor, dimethachlor and related compounds.

Die neuen Verbindungen werden in an sich bekannter Weise hergestellt.The new compounds are prepared in a manner known per se.

Man setzt dazu ein Pyridinderivat der Formel

Figure imgb0004
A pyridine derivative of the formula is used
Figure imgb0004

(A gleich Halogen, insbesondere Chlor, Fluor oder N02)(A is halogen, especially chlorine, fluorine or N0 2 )

mit einem Phenol oder Phenolat der Formel

Figure imgb0005
bzw.
Figure imgb0006
 with a phenol or phenolate of the formula
Figure imgb0005
 respectively.
Figure imgb0006

(M gleich 1 Äquivalent eines Kations, vorzugsweise Na+, K+, 1/2 Ca2+) um.(M equals 1 equivalent of a cation, preferably Na + , K + , 1/2 Ca 2 +).

Die Umsetzung der Verbindungen II und Illa bzw. III b erfolgt bei Temperaturen zwischen der Umgebungstemperatur und etwa 160°C. Man arbeitet vorzugsweise in polaren Lösungsmitteln wie Aceton, Butan-2-on, Acetonitril, Dimethylformamid, Dimethylsulfoxid bei Raumtemperatur oder mäßig erhöhter Temperatur. Bei der Umsetzung der Phenole gibt man säurebindende Mittel, z.B. Alkalicarbonate, etwa Na2CO3, K2C03, oder Alkali- oder Erdalkalihydroxide (NaOH, KOH, Ca(OH)2 zu- Um eine günstige Ausbeute zu erzielen, kann es vorteilnaft sein, das Phenol bzw. dessen Salze und/oder das säurebindende Mittel im Überschuß einzusetzen.The reaction of the compounds II and Illa or III b takes place at temperatures between the ambient temperature and about 160 ° C. It is preferably carried out in polar solvents such as acetone, butan-2-one, acetonitrile, dimethylformamide, dimethyl sulfoxide at room temperature or moderately elevated temperature. In the reaction of the phenols are one acid-binding agent, for example alkali metal carbonates, such as Na 2 CO 3, K 2 C0 3, or alkali or alkaline earth (NaOH, KOH, Ca (OH) 2 supply in order to achieve a favorable yield, it may be advantageous to use the phenol or its salts and / or the acid-binding agent in excess.

Die Ausgangsstoffe der Formeln II, Illa und Illb sind bekannt oder können analog den bekannten Verbindungen erhalten werden.The starting materials of the formulas II, Illa and Illb are known or can be obtained analogously to the known compounds.

Die Verbindunen der Formel werden für die Anwendung im Pflanzenschutz mit gebräuchlichen Hilfs- und/ oder Trägerstoffen zu üblichen Formulierungen verarbeitet.The compounds of the formula are processed into customary formulations for use in crop protection with customary auxiliaries and / or carriers.

Die Aufwandmengen bei der Anwendung als Herbizide liegen für die neuen Verbindungen im allgemeinen zwischen etwa 0, 05 und 2 kg, vorzugsweise 0, 1 und 1 kg, pro Hektar, je nach der verwendeten Substanz und dem zu bekämpfenden Unkraut. In Kombination mit anderen Herbiziden genügen im allgemeinen noch geringere Mengen (bis hinunter zu etwa 0, 03 kg/ha) der er-findungsgemäßen Verbindungen. Die nachstehenden Zubereitungen stellen beispiele für die Formulierung der neuen herbiziden Mittel dar (Angaben in Gewichtsprozent):

  • a) Suspensionspulver 1
    • 25 % Wirkstoff gemäß Formel
    • 55 % Kaolin
    • 9 % Ligninsulfonat als Dispergiermittel
    • 1 % Natriumtetrapropylenbenzolsulfonat als Netzmittel
  • b) Suspensionpulver 2
    • 80 % Wirkstoff gemäß Formel
    • 8 % Calciumligninsulfonat
    • 5 % kolloidale Kieselsäure
    • 5 % Natriumsulfat
    • 2 % Natriumdiisobutylnaphtinsulfonat
  • c) Emulsionskonzentrat
    • 40 % Wirkstoff gemäß Formel 1
    • 25 % Sellsol A (flüssiges Gemisch aromatischer Kohlenwasserstoffe)
    • 25 % N-Methylpyrrolidon
    • 10 % Emulsogen 140 (anionenaktiver

    Emulgator)
The application rates as herbicides for the new compounds are generally between about 0.05 and 2 kg, preferably 0.1 and 1 kg, per hectare, depending on the substance used and the weed to be controlled. In combination with other herbicides, generally even smaller amounts (down to about 0.03 kg / ha) of the compounds according to the invention are sufficient. The following preparations are examples of the formulation of the new herbicidal compositions (percentages by weight):
  • a) Suspension powder 1
    • 25% active ingredient according to the formula
    • 55% kaolin
    • 9% lignin sulfonate as a dispersant
    • 1% sodium tetrapropylene benzene sulfonate as wetting agent
  • b) suspension powder 2
    • 80% active ingredient according to the formula
    • 8% calcium lignin sulfonate
    • 5% colloidal silica
    • 5% sodium sulfate
    • 2% sodium diisobutyl naphthenesulfonate
  • c) emulsion concentrate
    • 40% active ingredient according to Formula 1
    • 25% Sellsol A (liquid mixture of aromatic hydrocarbons)
    • 25% N-methyl pyrrolidone
    • 10% Emulsogen 140 (more anion active

    Emulsifier)

Die unter a) bis c) angegebenen Konzentrate werden für die Anwendung mit Wasser auf etwa 0,05 bis 5 Gewichtsprozent verdünnt.The concentrates specified under a) to c) are diluted with water to about 0.05 to 5 percent by weight for use.

Die Wirkung der neuen Verbindungenwurde im Gewächshausversuch mit der Aufwandmenge 2 kg/ha geprüft (Vorauflaufwerte).The effect of the new compounds was tested in a greenhouse test at a rate of 2 kg / ha (pre-emergence values).

Als Vergleich diente A (= 4-(2, 4-Dichlorphenoxy)pyridin nach der DE-OS 15 43 736.A (= 4- (2,4-dichlorophenoxy) pyridine according to DE-OS 15 43 736 was used as a comparison.

Die Bewertungerfolgte nach den neunstufigen Bemitierungsschlüssel, wobei 1 = 100 % Wirkung, 9 = keine Wirkung bedeutet.

Figure imgb0007

  • • SIN = Sinapis alba
  • LYC = Lycopersicum esculentum
  • ECH = Echinocloa crus galli
  • Mit der guten Wirksamkeit der neuen

Verbindungen verbindet sich eine gute Verträglichkeit in zahlreichen Kulturen (z.B. Hafer, Weizen, Gerste, Kartoffeln, Soja, Baumwolle, Erbse), wodurch ein selektiver Einsatz ermöglicht wird.The evaluation was carried out according to the nine-level assessment key, where 1 = 100% effect, 9 = no effect.
Figure imgb0007
  • • SIN = Sinapis alba
  • LYC = Lycopersicum esculentum
  • ECH = Echinocloa crus galli
  • With the good effectiveness of the new

Connections combine good tolerance in numerous crops (e.g. oats, wheat, barley, potatoes, soybeans, cotton, peas), which enables selective use.

Die Anwendung kann sowohl vor wie auch nach dem Auflaufen erfolgen. Werden die neuen Wirkstoffe allein angewendet, so geschieht das vorzugsweise vor dem Auflaufen.The application can take place both before and after emergence. If the new active ingredients are used alone, this is preferably done before emergence.

Für Kombinationen, vor allen für die Nachauflaufbehandlung, eignen sich besonders

  • 1. Wuchsstoffherbizide, etwa 2, 4-DP, MCPA, CMPP;
  • 2. Kontaktherbizide, etwa loxynil, Bromoxynil, Bentazon, Bromphenoxim, Dinoterb;
  • 3. Grasherbizide, etwa Isoproturon, Diclofopmethyl. Die folgenden Beispiele sollen die erfindungsgemäßen Herstellverfanren näher erläutern, ohne sie zu beschränken:
For combinations, especially for post-emergence treatment, are particularly suitable
  • 1. Growth herbicides, about 2,4-DP, MCPA, CMPP;
  • 2. contact herbicides, such as loxynil, bromoxynil, Bentazone, bromophenoxime, dinoterb;
  • 3. Grass herbicides, such as isoproturon, diclofopmethyl. The following examples are intended to explain the manufacturing processes according to the invention in more detail without restricting them:

Beispiel 1example 1

2, 6-Dichlor-4- (2-chlor-4-tri fluormethylphenoxy)pyridin2,6-dichloro-4- (2-chloro-4-tri fluoromethylphenoxy) pyridine

Zu einer Suspension von 19,65 g (0,1 Mol) 2-Chlor-4-trifluormethyl-phenol und 19,29 g (0,1 Mol) 2,6To a suspension of 19.65 g (0.1 mol) of 2-chloro-4-trifluoromethyl-phenol and 19.29 g (0.1 mol) of 2.6

Dichlor-4-mitropyridin in 30 ml Dimethylformamid werden unter Eiskühlung und Rühren portionsweise 16,5 g (0,12 Mol) K2CO3 hinzugefügt. Nach 2-stüdigem Rühren bei Raumtemperatur wird die Mischung in 250 ml Eiswasser eingerüht. Zunächst scheidet sich ein Öl ab, das nach einiger Zeit kristallisiert. Das Produkt wird abgesaugt, mit Wasser gewaschen und anschließend in Chloroform gelöst. Man schüttelt mit Wasser, trennt die organische Phase ab und engt diese nach dem Trocknen mit Na2S04 ein. Man erhält 25,3 g (75%) farblose Sbstanz vom Schmelzpunkt 66° C.Dichloro-4-mitropyridine in 30 ml of dimethylformamide 16.5 g (0.12 mol) of K 2 CO 3 are added in portions with ice cooling and stirring. After stirring for 2 hours at room temperature, the mixture is stirred into 250 ml of ice water. First, an oil separates, which crystallizes after some time. The product is filtered off, washed with water and then dissolved in chloroform. It is shaken with water, the organic phase is separated off and concentrated after drying with Na 2 S0 4 . 25.3 g (75%) of a colorless substance with a melting point of 66 ° C. are obtained.

Beispiel 2Example 2

2-Chlor-6-methyl-4-(2-chlor-4-trifluormethylphenoxy)pyridin2-chloro-6-methyl-4- (2-chloro-4-trifluoromethylphenoxy) pyridine

Eine Lösung von 19,65 g (0,1 Mol) 2-Chlor-4-trifluormethyl-phenol sowie 17, 25 g (0,1 Mol) 2-Chlor-6-methyl-4-nitro-pyridin in 40 ml Dimethylformamid wird unter Rühren portionsweise mit 16,5 g (0,12 Mol) K2C03 versetzt, auf 80°C erwärmt und 3 Stunden bei dieser Temperatur gehalten. Nach dem Abkühlen gießt man auf 200 ml Eiswasser und extrahiert mit CHCI3. Die organische Phase wird abgetrennt, mit Wasser gewaschen, mit Na2S04 getrocknet und eingeengt. Der Rückstand wird durch Säulenchromatographie (Kieselgel) gereinigt. Man erhält ein zähes Öl, das nach einiger Zeit kristallisiert. Ausbeute: 20,9 g (65% d.Th.), Fp. 75° C.A solution of 19.65 g (0.1 mol) of 2-chloro-4-trifluoromethyl-phenol and 17.25 g (0.1 mol) of 2-chloro-6-methyl-4-nitro-pyridine in 40 ml of dimethylformamide 16.5 g (0.12 mol) of K 2 CO 3 are added in portions with stirring, heated to 80 ° C. and kept at this temperature for 3 hours. After cooling, it is poured onto 200 ml of ice water and extracted with CHCI 3 . The organic phase is separated off, washed with water, dried with Na 2 S0 4 and concentrated. The residue is purified by column chromatography (silica gel). A viscous oil is obtained which crystallizes after some time. Yield: 20.9 g (65% of theory), mp. 75 ° C.

Analyse: C13H8CI2F3NO (322.11)

Figure imgb0008
Analysis: C 13 H 8 CI 2 F 3 NO (322.11)
Figure imgb0008

Beispiel 3Example 3

2-Chlor-4- (2-chlor-4-trifluormethylphenoxy) - pyridin2-chloro-4- (2-chloro-4-trifluoromethylphenoxy) pyridine

Eine Lösung von 2,95 g (0, 015 Mol) 2-Chlor-4-trifluormethylphenol sowie 2, 2 g (0, 015 Mol) 2-Chlor-4-nitro-pyridin in 10 ml Dimethylformamid wird unter Rühren portionsweise mit 2,48 g (0,018 Mol) K2C03 versetzt, 1 Stunde bei Raumtemperatur und 1,5 Stunden bei 80°C gerührt. Anschließend wird auf Eiswasser gegossen und mit Chloroform extranert. Die organische Phase wird abgetrennt, mit 2 n NaOH und Wasser gewaschen, mit Na2S04 getrocknet und eingeengt.A solution of 2.95 g (0.015 mol) of 2-chloro-4-trifluoromethylphenol and 2.2 g (0.015 mol) of 2-chloro-4-nitro-pyridine in 10 ml of dimethylformamide is added in portions with 2 , 48 g (0.018 mol) of K 2 CO 3 were added, the mixture was stirred at room temperature for 1 hour and at 80 ° C. for 1.5 hours. It is then poured onto ice water and extranated with chloroform. The organic phase is separated off, washed with 2N NaOH and water, dried with Na 2 S0 4 and concentrated.

Man erhält ein farbloses Öl.A colorless oil is obtained.

Analyse: C16H6CI2F3NO

Figure imgb0009
Analysis: C 16 H 6 CI 2 F 3 NO
Figure imgb0009

1 H-NMR (CDCI3, ppm)1 H-NMR (CDCI 3 , ppm)

Protonen im Pyridinteil: 1 Proton bei 8,22 ppm, 2 Protonen bei 6,71. Protonen im Phenylreil: je 1 Proton bei 7,76, 7,56 und 7,22 ppm.Protons in the pyridine part: 1 proton at 8.22 ppm, 2 protons at 6.71. Protons in the phenyl range: 1 proton at 7.76, 7.56 and 7.22 ppm.

Beispiel 4Example 4

2-Chlor-6-methoxycarbonyl-4-(2-chlor-4-trifluormethylphenoxy) - pyridin2-chloro-6-methoxycarbonyl-4- (2-chloro-4-trifluoromethylphenoxy) pyridine

2,06 g (0,01 mol) 4,6-Dichlorpicolinsäuremethylester, 2,15 g (0,011 mol) 2-Chlor-4-trifluormethylphenol, 1,5 g pulverisiertes Kaliumcarbonat und 5 ml Dimethylformamid werden unter Rühren eine Stunde auf 120°C erwärmt. Das Gemisch erstarrt. Es wird mehrmals mit Eiswasser verrührt und dekantiert, dann mit verdünnter Essigsäure angesäuert und mit Essigester extrahiert. Die organische Phase wird abgetrennt, mit Wasser gewaschen und mit Natriumsulfat getrocknet. Man destilliert das Lösungsmittel ab und reinigt das resultierende Öl chromatographisch über 40 g Kieselgel (Laufmittel Diisopropylether). Das gereinigte Produkt ist ein helles Öl; Ausbeute 1,4 g (38 % d.Th.). Rf-Wert 0,48 (DC-Fertigplatten der Firma E. MERCK, Darmstadt, mit Kieselgel 60-F-254. Laufmittel Aceton/Diisopropylether 1: 2; die Flecken sind in ultravioletten Licht bei 254 µm sichtbar). Die DC-Fertigplatten des hier verwendeten Typs und das uv-Licht der genannten Wellenlänge dienten auch zur Bestimmung der übrigen Rf-Werte.2.06 g (0.01 mol) of 4,6-dichloropicolinic acid methyl ester, 2.15 g (0.011 mol) of 2-chloro-4-trifluoromethylphenol, 1.5 g of powdered potassium carbonate and 5 ml of dimethylformamide are stirred at 120 ° for one hour C warmed. The mixture solidifies. It is stirred several times with ice water and decanted, then acidified with dilute acetic acid and extracted with ethyl acetate. The organic phase is separated off, washed with water and dried with sodium sulfate. The solvent is distilled off and the resulting oil is purified by chromatography over 40 g of silica gel (mobile phase diisopropyl ether). The cleaned product is a light oil; Yield 1.4 g (38% of theory). Rf value 0.48 (ready-made DC plates from E. MERCK, Darmstadt, with silica gel 60-F-254. Solvent acetone / diisopropyl ether 1: 2; the spots are visible in ultraviolet light at 254 µm). The DC prefabricated plates of the type used here and the uv light of the stated wavelength also served to determine the other Rf values.

Die folgenden Verbindungen können beispielsweise gemäß der Erfindung erhalten werden:

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
 The following compounds can be obtained, for example, according to the invention:
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015

Claims (8)

1. Compounds of formula
Figure imgb0020
wherein
W and X, which may be the same or different, represent H, F, Cl, Br, J, NO2 or an optionally fluorineor chlorine-substituted C1-C4 alkyl group,
Y represents H, F, Cl, Br or an optionally fluorineor chlorine-substituted C1-C4 alkyl group,
Z represents F, Cl, Br, an optionally fluorine- or chlorine-substituted C1-C4 alkyl group or COOH or COO-(C1-C4 alkyl)

and
n represents 0 or 1.
2. Compounds as claimed in claim 1 wherein W represents H, F, Cl, CHg, CF3 or N02, X represents H, F, Cl, CH3, C3 or N02, Y represents H, F, Cl, CF3, CCI3 or CH3 and Z r;presents F, Cl, CF3, CH3 or COOH.
3. Compounds as claimed in claim 1 or 2, characterised in that n represents the number 0.
4. Biocidal, more particularly herbicidal agents, characterised in that they contain a compound as claimed in claim 1, 2 or 3.
5. Use of compounds as claimed in claim 1, 2 or 3 for controlling weeds.
6. Process for preparing compounds as claimed in claim 1, characterised in that a pyridine derivative of formula
Figure imgb0021
(wherein A represents halogen particularly chlorine or fluorine, or N02)
in reacted with a phenol or phenoxide of formula
Figure imgb0022
ou
Figure imgb0023
(wherein M equals 1 equivalent of a cation) with an acid-binding agent being added if phenol is used.
7. Herbicidal agents, characterised in that they contain, as active constituents, not only a compound as claimed in claim 1, 2 or 3 but also chlortoluron or a related urea, terbutryn or a related triazine derivative, or trifluralin or a related compound, alachlor or dimethachlor, 2,4-DP, MCPA, CMPP, ioxynil, bromoxynil, bentazone, bromophenoxime, dinoterb, isoproturon or diclofop-methyl.
8. Use of a compound as claimed in claim 1, 2 or 3 in conjunction with chlortoluron or a related urea, terbutryn or a related triazine derivative, trifluralin or a related compound, alachlor or dimethachlor, 2,4-DP, MCPA, CMPP, ioxynil, bromoxynil, bentazine, bromophenoxime, dinoterb, isoproturon or diclofop-methyl for controlling weeds.
EP83100757A 1982-02-13 1983-01-27 Pyridine derivatives, their preparation and use Expired EP0086375B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100757T ATE19068T1 (en) 1982-02-13 1983-01-27 PYRID DERIVATIVES, THEIR PREPARATION AND USE.

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DE3205150 1982-02-13

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GB8624831D0 (en) * 1986-10-16 1986-11-19 Ici Plc Insecticidal ethers
US5399564A (en) * 1991-09-03 1995-03-21 Dowelanco N-(4-pyridyl or 4-quinolinyl) arylacetamide and 4-(aralkoxy or aralkylamino) pyridine pesticides
DE4331181A1 (en) * 1993-09-14 1995-03-16 Hoechst Schering Agrevo Gmbh Substituted pyridines, processes for their preparation and their use as pesticides and fungicides
US7067664B1 (en) 1995-06-06 2006-06-27 Pfizer Inc. Corticotropin releasing factor antagonists
KR100271513B1 (en) * 1995-06-06 2000-12-01 디. 제이. 우드 Process for converting 2, 4-dichloropyridines into 2- aryloxy-4-chlropyridines

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US3576616A (en) * 1969-05-15 1971-04-27 Monsanto Co Herbicidal compositions and methods
US3888932A (en) * 1972-03-14 1975-06-10 Rohm & Haas Herbicidal 4-trifluoromethyl-4-nitrodiphenyl ethers
DE2862462D1 (en) * 1977-08-12 1985-05-15 Ici Plc 2-CHLORO-5-TRICHLOROMETHYLPYRIDINE
JPS54163582A (en) * 1978-06-09 1979-12-26 Ishihara Mining & Chemical Co 22phenoxyy55 trifluoromethypiridine compound
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IL67885A0 (en) 1983-06-15
US4655824A (en) 1987-04-07
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DK155997C (en) 1989-11-06
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ATE19068T1 (en) 1986-04-15

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